From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond

Nature Communications
Chelladurai GanesamoorthyStephan Schulz

Abstract

Neutral stibinyl and bismuthinyl radicals are typically short-lived, reactive species. Here we show the synthesis and solid-state structures of two stable stibinyl [L(Cl)Ga]2Sb· 1 and bismuthinyl radicals [L(I)Ga]2Bi· 4, which are stabilized by electropositive metal centers. Their description as predominantly metal-centered radicals is consistent with the results of NMR, EPR, SQUID, and DFT studies. The Lewis-acidic character of the Ga ligands allow for significant electron delocalization of the Sb- and Bi- unpaired radical onto the ligand. Single-electron reduction of [L(Cl)Ga]2Sb· gave LGaSbGa(Cl)L 5, the first compound containing a Ga=Sb double bond. The π-bonding contribution is estimated to 9.56 kcal mol-1 by NMR spectroscopy. The bonding situation and electronic structure is analyzed by quantum mechanical computations, revealing significant π backdonation from the Sb to the Ga atom. The formation of 5 illustrates the high-synthetic potential of 1 for the formation of new compounds with unusual electronic structures.

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Citations

Apr 18, 2018·Chemistry : a European Journal·Julia KrügerStephan Schulz
Jun 14, 2018·Chemistry : a European Journal·Marcella E Desat, Robert Kretschmer
Aug 1, 2018·Chemical Communications : Chem Comm·Marcel SchorppIngo Krossing
Jul 30, 2019·Chemistry : a European Journal·Monika KořenkováLibor Dostál
Nov 23, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Juliane SchoeningStephan Schulz
Jan 17, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Mingdong ZhongHerbert W Roesky
Jan 24, 2020·Chemical Communications : Chem Comm·Haiyan CuiXinping Wang
Sep 26, 2019·Angewandte Chemie·Mahendra K SharmaRajendra S Ghadwal
Feb 28, 2020·Chemical Communications : Chem Comm·Mahendra K SharmaRajendra S Ghadwal
Feb 13, 2020·Angewandte Chemie·Christoph HellingStephan Schulz
Feb 13, 2020·Chemistry : a European Journal·Crispin Lichtenberg
Aug 20, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·George E Cutsail
Jul 3, 2020·Angewandte Chemie·Daniel W N WisonJose Manuel Goicoechea
Jul 15, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Christoph HellingStephan Schulz
Dec 4, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Marcella E Desat, Robert Kretschmer
Apr 22, 2020·Nature Chemistry·Chelladurai GanesamoorthyStephan Schulz
Jun 24, 2020·Chemistry : a European Journal·Jacqueline RamlerCrispin Lichtenberg
Oct 22, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Daniel W N WilsonJose M Goicoechea
May 20, 2020·Chemistry : a European Journal·Christoph HellingStephan Schulz
Jul 27, 2020·Chemistry : a European Journal·Joshua W M MacMillanSaurabh S Chitnis
Oct 10, 2020·Angewandte Chemie·Bin LiStephan Schulz
Nov 18, 2020·Angewandte Chemie·Julia KrügerStephan Schulz
Dec 17, 2020·Chemistry : a European Journal·Anna HanftCrispin Lichtenberg
Mar 11, 2021·Journal of the American Chemical Society·Malte FischerChristian Hering-Junghans
Apr 17, 2021·Chemical Communications : Chem Comm·Crispin Lichtenberg
Aug 6, 2021·Chemical Science·Veronika HeinlManfred Scheer
Jul 25, 2018·Inorganic Chemistry·Chelladurai GanesamoorthyStephan Schulz
Mar 15, 2018·Journal of the American Chemical Society·Christoph HellingStephan Schulz
Dec 29, 2020·Journal of the American Chemical Society·Oleksandr KysliakRobert Kretschmer
Jul 30, 2021·Angewandte Chemie·Mahendra K SharmaStephan Schulz
Aug 13, 2021·Angewandte Chemie·Joey FeldJose M Goicoechea
Sep 4, 2021·Angewandte Chemie·Samuel NeesChristian Hering-Junghans
Dec 24, 2021·Inorganic Chemistry·Julia KrügerStephan Schulz

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Methods Mentioned

BETA
electron
X-ray
electron paramagnetic resonance
NMR

Software Mentioned

ORCA

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